[0001] This invention relates to an ultrasonographic process. More specifically, this invention
is directed to a process of forming a visible image in a silver halide element through
the use of imagewise ultrasonic alteration of a silver halide emulsion layer and conversion
of such ultrasonically induced alteration of the emulsion layer to a viewable image.
[0002] The term "ultrasonic radiation" is employed herein to designate pressure-rarefaction
waves differing from sound waves in exhibiting higher frequencies and shorter wavelengths.
Other grammatical variations of the nomenclature concerning ultrasonics that are used
herein are consistent with those used in the art. Specifically, these terms are suggested
by P. J. Ernst in the Journal of the Accoustical Society of America, Vol. 22, No.
1, in an article entitled "Ultrasonography", pp. 80-83, January 1951.
[0003] The prior state of the art with respect to the action of ultrasound on silver halide
photographic elements is reviewed by M. E. Arkhangel'skii, Soviet Physics-Acoustics,
Vol. 12, No. 3, "Action of Ultra- sound on the Process of Photographic Development
and Fixing", pp. 241-248, January-March 1967. The ability of ultrasound exposure to
produce a latent image in silver halide emulsions has been previously recognized as
reported by Arkhangel'skii. However, power level requirements to achieve ultrasonic
imaging have been quite high, it is uncertain as to whether the ultra- sound directly
produces the latent image or stimulates other effects, such as cavitation-stimulated
lumine- sence, which produce the latent image. It has been recognized that higher
maximum densities are attainable for a given power level of ultrasonic exposure when
the photographic element is in contact with a photographic developer. Arkhangel'skii
observed that if the photographic element is first light exposed and then ultrasonically
exposed in a developer, the ultrasonic time and intensity to produce a density obtainable
in the absence of light exposure decrease to a few minutes and a few watts per square
centimeter, respectively.
[0004] It has been a problem in the art that ultrasonic exposure requirements of silver
halide photographic elements, even with the most responsive techniques known, have
remained unattractively high. For example, such techniques have required intensity
and time levels of ultrasonic exposure which are objectionable to many non-destructive
testing applications, such as mammographic examination with ultrasound as described
in U.S. Patent 3,765,403.
[0005] The present invention relates to an ultrasonographic process for preparing visible
images that can be carried out with low levels of ultrasonic exposure. The process
uses an element comprised of a support having a silver halide emulsion layer, and
which process comprises exposing the element to ultrasound in an image pattern while
the element is in contact with a liquid, and developing the element with a silver
halide developer to produce a
lvisible image defined by the ultrasonic exposure, characterized in that the silver
halide emulsion contains internally fogged silver halide grains, the liquid is a transport
liquid for a diffusible solute capable of rendering the internally fogged silver halide
grains developable in a surface developer. The exposure to ultrasound accelerates
imagewise diffusion of the solute into contact with the internally fogged silver halide
grains.
[0006] The invention can be further explained by reference to the following detailed description
considered in conjunction with the drawings, in which
Figures 1 and 3 through 6 are plots of density versus ultrasonic exposure and
Figure 2 is a plot of density versus immersion time.
[0007] To form an ultrasonograph according to this process any
3ilver halide element can be employed comprised of a support and, coated thereon, at
least one silver halide emulsion layer which contains internally fogged silver halide
grains. Such elements are hereinafter designated internally fogged silver halide elements.
[0008] The internally fogged silver halide elements are capable of producing a visible density
when developed in an internal developer and are sufficiently free of surface fog that
they produce a readily visually discernable lower density when developed in a surface
developer as compared with an internal developer. For instance, the internally fogged
silver halide elements are preferably capable of producing a density of at least 0.5,
most preferably at least 1.0, when processed for 5 minutes in Reference Internal Developer
A at 25°C. When processed for 5 minutes in Reference Surface Developer B at 25°C such
elements are preferably capable of producing a density of at least 0.2, most preferably
at least 0.8, less than when comparably processed with Reference Internal Developer
A.
[0009] In a specifically preferred form,the internally fogged elements are sufficiently
free of surface fog that they produce a density of less than 0.1 when processed for
5 minutes in reference Surface Developer B at 25°C.
Reference Internal Developer A
[0010]
Reference Surface Developer B
[0011]
[0012] Internally fogged silver halide elements suitable for use in this process can be
provided by the selection or modification of known silver halide photographic elements.
For example, photographic elements which contain both surface-sensitive emulsions
and internally fogged, internal latent image-forming emulsions are disclosed by U.S.
Patents 2,996,382, 3,178,282, 3,397,987; 3,705,858; 3,695,881; Research Disclosure,
Vol., 134, June 1975, Item 13452; Millikan et al U.S. Patent Office Defensive Publication
T-0904017, April 21, 1972 and Research Disclosure, Vol. 122, June 1974, Item 12233.
The surface-sensitive and internally fogged emulsions are blended or coated in separate
layers. Where the coating coverage of the internally fogged emulsions is sufficient
to provide a density of at least about 0.5 in Reference Internal Developer A, as described
above, these photographic elements can be employed without further modification .
in this process. In a preferred form these photographic elements are modified to omit
the surface-sensitive emulsions, since they do not contribute to imaging in the present
process and offer the disadvantage of rendering the elements light-sensitive. It is
preferred to increase the coating coverages of the internally fogged emulsions in
these elements, since these emulsions are alone being relied upon to produce a visible
image, rather than working in combination with the surface-sensitive emulsions as
these elements are conventionally employed.
[0013] The internally fogged silver halide elements employed in this process can also be
prepared merely by exposing conventional photographic elements of the type which form
internal latent images. By uniform light exposure, for example, such conventional
internal latent image-forming elements are converted to internally fogged silver halide
elements. Conventional internal latent image-forming emulsions and photographic elements
are illustrated by U.S. Patents 2,592,250; 3,206,313; 3,317,322; 3,761,276; 3,767,413;
3,979,213 and 3,367,778.
[0014] Particularly preferred internal latent image-forming emulsions are those containing
converted-halide grains, as described in U.S. Patent 2,592,250. The term "converted-halide
silver halide grains" is employed herein as a recognized word of art denoting silver
halide grains prepared by forming an emulsion of silver salt grains comprised of a
silver salt more soluble in water than silver bromide, and "converting" at least a
portion of such grains to silver bromide or silver bromoiodide salts. The preferred
converted-halide silver halide grains employed in the practice of this invention have
a halide content of-at least 50 mole percent, most preferably at least 80 mole percent,
bromide and up to 10 mole percent, most preferably less than 5 mole percent, iodide,
any remaining halide being chloride. Especially good results are obtained with converted-halide
silver halide grains containing about 93 mole percent bromide and about 10 mole percent
chloride.
[0015] The silver halide grains can be internally fogged as they are formed, but it is generally
more convenient to expose the emulsions or elements with light after they are formed.
In converting the conventional internal latent image-forming elements to internally
fogged elements by light exposure it is preferred that exposures be sufficient to
produce a maximum density when the elements are thereafter developed in an internal
developer, such as in Reference Internal Developer A as described above. The internal
latent image-forming elements are substantially free of surface fog, and, since they
form internal latent images upon exposure, after light exposure and processing in
a surface developer, such as Reference Surface Developer B as described above, they
yield densities substantially below the preferred 0.1 minimum density levels. The
foregoing density characteristics are, of course, those which the emulsion layers
exhibit prior to ultrasonic exposure.
[0016] One or more photographic hydrophilic vehicle materials are present in combination
with the internally fogged silver halide grains to form the emulsion layer or layers
of the elements. The vehicles are also present in layers, if any, which overlie the
emulsion layers. The vehicles perform the various functions conventionally performed
in photographic elements-- e.g., peptizing and binding. The vehicles employed are
those which are penetrable by conventional aqueous photographic processing liquids,
such as developers. As employed in the practice of this invention the vehicles perform
the additional function of acting a. a barrier to impede diffusion of solute to the
internally fogged silver halide grains in the absence of ultrasound.
[0017] It is generally preferred to employ hydrophilic colloids alone or in combination
with other materials as vehicles. Suitable hydrophilic materials include both naturally
occurring substances such as proteins, protein derivatives, cellulose derivatives--e.g.,
cellulose esters, gelatin--e.g., alkali-treated gelatin (cattle bone or hide gelatin)
or acid-treated gelatin (pigskin gelatin), gelatin derivatives--e.g., acetylated gelatin,
phthalated gelatin and the like, polysaccharides such as dextran, gum arabic, zein,
casein, pectin, collagen derivatives, collodion, agar-agar, arrowroot, albumin and
the like.
[0018] The element layers can also contain alone or in combination with hydrophilic water
permeable colloids as vehicles or vehicle extenders (e.g., in the form of latices),
synthetic polymeric peptizers, carriers and/ or binders such as poly(vinyl lactams),
acrylamide polymers, polyvinyl alcohol and its derivatives, polyvinyl acetals, polymers
of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates,
polyamides, polyvinyl pyridine, acrylic acid polymers, maleic anhydride copolymers,
polyalkylene oxides, methacrylamide copolymers, polyvinyl oxazoli- dinones, maleic
acid copolymers, vinylamine copolymers, methacrylic acid copolymers, acryloyloxyalkylsulfonic
acid copolymers, sulfoalkylacrylamide copolymers, polyalkyleneimine copolymers, polyamines,.N,N-dialkylaminoalkyl
acrylates, vinyl imidazole copolymers, vinyl sulfide copolymers, halogenated styrene
polymers, amineacrylamide polymers, polypeptides and the like.
[0019] It is a significant advantage of this process that the internally fogged silver halide
elements in their preferred form can be handled in room light and that nc requirement
of either exposing the elements to light or protecting the elements from ordinary
room light, such as incandescent lighting, is imposed on the process. Thus, there
is nc requirement for darkroom processing, nor is there any required light exposure
step to complicate subsequent processing steps or the apparatus employed in their
performance.
[0020] Although the foregoing discussion has been in terms of light exposure, it is appreciated
that these comments are generally applicable to forms of electromagnetic radiation
conventionally employed in the exposure of photographic elements. For example, in
addition to light within the visible spectrum or within a selected portion thereof,
other wavelengths of electromagnetic radiation, such as ultraviolet light, infrared
radiation, X-rays and gamma rays, are particularly contemplated for converting internal
latent image-forming silver halide photographic elements into internally fogged elements.
[0021] The internally fogged silver halide element is in contact during ultrasonic exposure
with a transport liquid, which serves two distinct functions. First, the transport
liquid acts as a medium for the transmission of ultrasound. Liquids transmit ultrasonic
energy more efficiently (that is, with less attenuation) than gaseous media. Second,
the transport liquid serves as a reservoir for a solute which can be initially present
in the internally fogged photographic element or the transport liquid.
[0022] The transport liquid is related to the internally fogged emulsion layer(s) of the
element so that a diffusion path for the solute is available between the transport
liquid and the internally fogged emulsion layer(s). This can be accomplished by relating
the transport liquid and the internally fogged element i:. any conventional manner
of bringing a developer solution into contact with a photographic element for purposes
of photographic processing. In a simple form the transport liquid can be spread on
the emulsion coated surface of the element by coating, or the element can be immersed
in the transport liquid.
[0023] The specific choice of a transport liquid to be placed in contact with the internally
fogged element will be influenced, of course, by the specific solute chosen. Where
the solute is being transported in ionized form, it is preferred that the transport
liquid be a polar solvent. Water is a preferred polar solvent for use in the practice
of this process. However, any polar solvent or combination of polar solvents known
to be compatible with the elements and solute can be employed. Exemplary useful polar
solvents in addition to water include water-miscible alcohols, ketones and amides
(e.g., acetone, phenol, ethyl alcohol, methyl alcohol, iospropyl alcohol, ethylene
glycol, N,N-dimethylacetamide, and methyl ethyl ketone), tetrahydrofuran, N-methyl-2-pyrrolidone,
dimethylsulfoxide and mixtures of the above, with or without water. Generally any
transport liquid can be employed which is chemically compatible with the solute and
the internally fogged element.
[0024] Any solute can be employed in the practice of this invention which, following contact
with the internally fogged silver halide grains, is capable of rendering them developable
in a surface developer, such as Reference Surface Developer B. Iodide ions are particularly
effective in rendering internally fogged silver halide grains developable in a surface
developer. It is known that silver iodide has a solubility product constant which
is approximately two orders of magnitude less than that of silver bromide and approximately
four orders of magnitude less than that of silver chloride. On the other hand, photographic
silver halide emulsions conventionally contain less than about 20 (typically less
than 10) mole percent silver iodide, based on total silver halide. What is believed
to occur when a photographic silver halide is brought into contact with iodide ions
in the presence of a transport liquid is that the iodide ions displace the bromide
and/or chloride atoms in the silver halide crystal lattice so that the much less soluble
silver iodide is formed. The iodide ions, being much larger than the bromide and/or
chloride atoms which they displace in the crystal lattice, disrupt the crystal structure
to the extent of opening the interior of the silver halide grains to contact with
a surface developer. Any convenient source of iodide ions can be employed as a solute
in the practice of this process. Where the transport liquid is water or an aqueous
medium, water soluble iodide salts can be employed, such as alkali iodide e.g., sodium
iodide, potassium iodide and lithium iodide. While suitable iodide concentrations
under varied conditions can be readily ascertained, as described below, it is typically
preferred to employ iodide ion concentrations of from about 100 to 1000, preferably
200 to 800, milligrams per liter of transport liquid. If the iodide solute is incorporated
in the element, it should be coated in a layer separate from the internally fogged
silver halide emulsion layer.
[0025] Known silver halide solvents can also be employed as solutes in the practice of this
process. Water soluble thiosulfates constitute a specifically preferred class of silver
halide solvents. Water soluble thiosulfates, particularly ammonium and alkali metal
thiosulfates, such as sodium and potassium thiosulfates, are commonly incorporated
in silver halide developers to provide the capability of developing internal latent
images. Thiosulfate concentrations in the transport liquid are preferred corresponding
to the concentrations in which thiosulfates are conventionally incorporated in internal
silver halide developers.
[0026] Another class of silver halide solvents are water soluble sulfur-containing compounds
of the type which have been conventionally employed as ripening agents when employed
in the formation of silver halide emulsions. Such sulfur-containing compounds include
water-soluble thioethers and thiocyanates.
[0027] Conventional thioethers, such as those disclosed in U.S. Patent 3,271,157 can be
employed. Certain of the preferred organic thioether silver halide solvents can be
represented by the formulas:
and
wherein: r and m are integers of 0 to 4; n is an integer of 1 to 4; p and q are integers
of 0 to 3; X is an oxygen atom (-0-), a sulfur atom (-S-), a carbamyl radical
a carbonyl radical
)r a carbonyl radical
or R and R' are ethylene oxide radicals (-O-CH
2CH
2-); Q and Z are hydroxy radicals (-OH), carboxy radicals, or alkoxy radicals (-O-alkyl)
wherein the alkyl group has 1 to 5 carbon atoms; and Q and Z can also be substituents
described for X linked to form a cyclic compound
[0028] Preferred organic thioether silver halide solvents include compounds represented
by the formulas:
and
wherein: r is an integer of 1 to 3; s is an integer of 1 to 2; R
2 is an alkylene radical having 1 to 5 carbon atoms and is preferably ethylene (-CH
2CH
2-); R
3 is an alkyl radical having 1 to 5 carbon atoms and is preferably ethyl; and R
4 is an alkylene radical having 1 to 5 carbon atoms and is preferably methylene (-CH
2-).
[0029] As an alternative to thioether silver halide solvents, thiocyanate salts can be used,
such as alkali metal, most commonly potassium, and ammonium thiocyanate salts. Conventional
thiocyanates can be employed, such as those disclosed in U.S. Patents 2,222,264, 2,448,534
and 3,320,069, as ripening agents.
[0030] Another useful class of silver halide solvents are pyridinium salts, such as those
disclosed in U.S. Patent 2,648,604. The preferred pyridinium salts to be employed
can be represented by the following general formula:
wherein D represents the atoms necessary to complete an unsubstituted pyridinium nucleus,
an alkoxy-substituted pyridinium nucleus, e.g., a 2-methoxy-, 3-methoxy-, 4-methoxy-,
2-ethoxy-, 3-ethoxy-, 2,4-dimeth- oxy-, 2,4-diethoxy-, 2,5-diethcxy-, or 3,5-diethoxy-
pyridinium nucleus; a picolinium nucleus, e.g., a 4-methyl-, 2-methyl-, or 3-methyl-pyridinium
nucleus; a lutidinium nucleus, e.g., a 2,3-dimethyl-, 2,4-dimethyl-, 2,5-dimethyl-,
2,6-dimethyl-, 3,4-dimethyl-, 3,5-dimethyl-, 2-ethyl-, 3-ethyl- or 4-ethyl-pyridinium
nucleus; a collidinium nucleus, e.g., a 2-propyl-, 2-isopropyl-, 4-methyl-2-ethyl-,
4-methyl-3-ethyl-, 2-methyl-4-ethyl-, 2-methyl-5-ethyl-, 2-methyl-6-ethyl-, 2,3,4-trimethyl-,
or 2,3,6-trimethyl-pyridinium nucleus, or a parvolinium nucleus, e.g., a 2-butyl-,
2-isobutyl-, 3,5-dimethyl-2-ethyl-, 2,6-dimethyl-3-ethyl-, 2,6-dimethyl-4-ethyl-,
2,4-diethyl- or 3,4-diethyl- pyridinium nucleus; wherein R is a short chain aliphatic
radical having not more than 5 carbon atoms, such as alkyl, e.g., methyl, ethyl, propyl,
butyl or amyl; chloro-or bromoalkyl, e.g., β-chloroethyl, β-bromoethyl, γ-chloropropyl
or y-bromopropyl; hydroxyalkyl, e.g., 6-hydroxyethyl, β-hydroxypropyl, or β,γ-dihydroxypropyl,
carboxymethyl; carbalkoxymethyl, e.g., carbomethoxymethyl, carbethcxymethyl or carbo-
propoxymethyl, carboxamidomethyl; N-substituted carboxamidomethyl, e.g., N,N-dimethylcarboxamidomethyl;
alkoxyalkyl, e.g., methoxymethyl, ethoxymethyl, ethoxyethyl or propoxymethyl; and
wherein X represents an anion such as chloride, bromide thiocyanate, methylsulfate
and thiocyanate.
[0031] In addition to the use of thioethers, thiosulfates, thiocyanates and pyridinium salts
as silver halide solvents, soluble sulfite salts, such as alkali sulfite salts, in
the presence of ultrasound are useful solvents for high chloride silver halide grains.
Higher chloride silver halide grains are those which are greater than 50 mole percent
chloride, based on total halide. However, sulfite solutes are not effective solvents
for silver bromide and silver bromoiodide grains.
[0032] The internally fogged silver halide element, in contact with the transport liquid
and solute, is imagewise exposed to ultrasonic radiation. This can be accomplished
using any conventional sonic camera which is capable of impinging ultrasonic radiation
on the element as an image receptor. In such a sonic camera a sonic source or transducer
(i.e., an emitter of ultrasonic radiation) and the element are spatially related so
that the ultrasonic radiation, unless interrupted, can impinge on the silver halide
emulsion layer(s) to be imagewise exposed. Between the sonic transducer and the internally
fogged element is interposed any means which will imagewise modulate the ultrasonic
radiation as it is received by the emulsion layer(s). In a simple form this can take
the form of an apertured template which absorbs or reflects the ultrasonic radiation
which strikes it and allows a portion of the ultrasonic radiation to pass through
the aperture to the element. Alternatively the reflected ultrasonic radiation can
be caused to impinge on the element. In a more sophisticated form the imaging means
can include combinations of sonic lenses and reflectors for focusing and directing
the ultrasonic radiation. In one application of this process an object whose ultrasonic
modulation characteristic is desired to be recorded is placed in the sonic camera
so that it intercepts ultrasonic radiation passing from the sonic transducer to the
element. For example, the ultrasonoscope described ir U.S. Patent 3,765,403, can be
readily adapted for use as a sonic camera in the practice of this invention merely
by locating the internally fogged element in one of the water tanks so that it is
impinged by the ultrasonic radiation which has passed through or been reflected by
the mamma under examination.
[0033] In a simple mode of practicing this process, a single transport liquid is in contact
with the sonic transducer and the internally fogged element and provides a medium
for transmission of ultrasound therebetween. In an alternative form the sonic transducer
can be contacted with one transport liquid and a second transport liquid can be in
contact with the internally fogged element with an ultrasonically transmitting partition,
such as a membrane, separating the two transport media. In still another form the
solute and a first transport liquid can be entirely within the emulsion layer(s) to
be imagewise exposed and a second transport liquid which is chemically compatible
with the internally fogged element can be placed in contact therewith to permit ultrasonic
exposure. For example, a polar solvent containing the solute can be imbibed into or
coated on the emulsion layer to be exposed and then the internally fogged element
immersed in a nonpolar liquid, such as cyclohexane, benzene, etc.
[0034] Except where rapid alteration of the developability as a function of contact with
the transport liquid and solute prohibits, it is preferred to allow the element at
least a few seconds, preferably at least 5 seconds, of contact with the transport
liquid before initiating ultrasonic exposure. It is within the invention to bring
the internally fogged silver halide element into contact with the transport liquid
first and then later to add the solute to the transport liquid reservoir. Delaying
ultrasonic exposure after initial contact with the transport liquid can be used to
enhance ultrasonographic response. The optimum delay period for a particular element
can be correlated to the contact period at which incipient alteration of the developability
of the element is observed in the solute selection test. For some elements alteration
of developability begins immediately upon contact with the transport liquid and solute,
and there is no advantage to delaying the ultrasonic exposure.
[0035] Some elements, such as those having film supports, directly absorb only a very small
fraction of the total ultrasonic radiation to which they are exposed, the rest passing
directly through the element. Accordingly, it is possible during ultrasonic exposure
to orient an internally fogged film element so that either the emulsion layer bearing
surface or the film support of the element is nearest to the sonic radiation source.
Also, one or a plurality of imaging emulsion layers can be coated on either or both
major surfaces of the film support and concurrently exposed. Further, it is possible
to stack two or more film elements so that ultrasonic radiation passes through them
sequentially during exposure. Of course, where precise focusing of the ultrasonic
radiation is desired, the number of film elements which will produce optimum images
may be limited. By way of contrast, photographic paper supports absorb almost all
of the ultrasonic imaging radiation to which they are exposed according to this process.
For elements having paper supports the silver halide emulsion layer must be on the
side nearest to the source of the ultrasonic radiation source. Better image quality
is obtained in all instances where the emulsion-flayer is on the face of the support
nearest the ultrasonic energy source.
[0036] Imagewise exposure of the internally fogged element in the sonic camera is at an
intensity and for a duration which is insufficient to produce a developable image
in the absence of the solute. The level of ultrasonic exposure is lower than that
which has been recognized in the art to produce ultrasonic images in the absence of
light or to render imagewise developable surface fogged silver halide elements. The
ultrasonic imaging exposure is itself insufficient to produce a variation in the development
of the internally fogged emulsion layer(s) of the element being exposed in the absence
of the solute. Successful imaging is readily achieved at ultrasonic exposures below
100 watt-sec/cm2 by this process.
[0037] Just as different photographic elements exhibit marked differences in their sensitivity
to electromagnetic exposure, different internally fogged elements will also exhibit
different sensitivities to ultrasonic radiation. By exposing internally fogged elements
to differing ultrasonic intensities and then performing the photographic processing
steps intended for use, the optimum ultrasonic exposure for a given internally fogged
element can be readily determined. In a manner analogous to light sensitometry using
a step tablet, it is possible to expose an internally fogged element simultaneously
in offset areas with an array of laterally spaced sonic transducers which are calibrated
to transmit ultrasonic radiation at predetermined stepped levels of intensity. Upon
photographic processing, densities produced by each transducer can be plotted against
ultrasonic exposure. This generates an ultrasonic characteristic curve for the particular
internally fogged element from which the optimum intensity of ultrasonic exposure
can be readily determined.
[0038] The determination can be repeated using differing durations of ultrasonic exposure,
if desired, although this is not usually necessary. In using photographic cameras
varied shutter speeds (exposure times) and f-stop settings (exposure intensities)
are available to the photographer to achieve a given exposure, since exposure is recognized
to be the mathematical product of exposure time and intensity. The proposition that
equal photographic exposures differing in intensity and duration produce similar photochemical
response is referred to as the photographic reciprocity law, and this law is generally
relied upon in photography in varying exposure times and intensities, although it
is recognized that many photographic elements exhibit significant reciprocity law
failure. By analogy to photography, various combinations of ultrasonographic exposures
as a mathematical product can be relied upon in a general way in accordance with a
reciprocity law of ultrasonic exposure which is analogous to the photographic reciprocity
law.
[0039] Any ultrasonic frequency heretofore employed in ultrasonography can be applied to
the practice of this process. For a given transport liquid the wavelength of the ultrasonic
radiation is reciprocally related to its frequency. Since best imaging results in
ultrasonography and ultrasonoscopy are recognized to be obtainable when the wavelength
of the ultrasonic imaging radiation is substantially shorter than the dimension of
the object or object feature to be imaged, it is generally preferred to operate at
shorter wavelengths and hence higher frequencies. For example, at a frequency of 1
megahertz ultrasonic radiation transmitted in water exhibits a wavelength in the order
of 1.5 millimeters. Accordingly, in obtaining ultrasono- graphs of objects or object
features of 1.5 millimeters in dimension it is preferred to operate substantially
above 1 megahertz, typically in the range of 2.5 to 100 megahertz. Frequencies in
the order of gigahertz are known in the art and can be employed, particularly when
microscopic image definition is required. The high operating frequencies are, of course,
advantageous since they effectively define both large and small objects and object
features, although increased absorptivity of many materials at higher frequencies
requires thinner object samples. In the prior art, ultrasonic exposures of photographic
elements have most typically occurred at lower frequencies in order to stimulate cavitation.
This process is not similarly limited.
[0040] The ultrasonic exposure of the photographic element can be constant in intensity
for the duration of expcsure or it can be varied in intensity. Pulsing of the ultrasonic
exposure can be achieved by continuously modulating the intensity of exposure, preferably
by interrupting ultrasonic exposure so that ultrasonic exposure is divided into separate
bursts or discrete pulses. It is contemplated to employ discrete pulses wherein the
duration of the pulses and the interval therebetween is less than a tenth of a second.
The duration of the ultrasonic pulse and the interval between pulses can be varied
independently, if desired. The minimum useful pulse and interval durations are limited
only by the capabilities of the ultrasonic emitters selected for use. Naturally, as
the pulses and intervals between pulses approach the frequency of the ultrasonic radiation,
continuous exposure will be approached as a limit.
[0041] In one specifically contemplated form of this process the internally fogged element
is contacted with the transport liquid and solute, ultrasonically imagewise exposed
and then developed in a surface developer. Development preferentially occurs in ultrasonically
exposed areas to produce a negative ultrasonic image. In one preferred form the transport
liquid is water, and the solute is dissolved in the water or is incorporated in the
element, such as in an overcoa; layer. In a specifically preferred form the internally
fogged element is immersed in a bath which consists essentially of water and the solute
which can be diffusing into the element during ultrasonic exposure. In an alternative
form a conventional viscosity increasing agent can be added to the transport liquid,
and it can be spread as a layer on the internally fogged element.
[0042] The term "surface developer" is employed in its art recognized usage to indicate
developers which are capable of developing silver halide grains containing a surface
latent image or surface fog, but not silver halide grains containing only an internal
latent image or internal fog. The surface developers can generally utilize any of
the silver halide developing agents, but the developer solution is sufficiently free
of water soluble iodide salts, water soluble thiocyanates, thioethers, thiosulfates
and pyridinium salts and any other solute which will disrupt or dissolve silver halide
grains to avoid revealing an internal latent image or internal fog during the contemplated
time of development.
[0043] In the foregoing mode of practicing this process, referred to as a sequential mode,
the ultrasonic exposure occurs in the presence of a transport liquid and a solute
in the absence of a silver halide developing agent, and the ultrasonically exposed
element is thereafter developed in a surface developer to achieve distinct advantages.
Surface development is substantially limited to those areas of the internally fogged
element which have been ultrasonically exposed. This is in direct contrast to obtaining
differential development of a surface fogged silver halide element as a result of
imagewise ultra-sound exposure. In the latter instance silver halide development occurs
in both ultrasonically exposed and background areas. In the sequential mode of practicing
this process a relatively low minimum density level in unexposed areas is obtainable,
since the internal fog sites within the silver halide grains are not accessible to
the surface developer. Further, there is no necessity of arresting development before
maximum image densities are obtained in order to avoid elevated minimum densities.
Finally, it is a surprising feature of this process that development of the internally
fogged element to produce a viewable image can be achieved using a surface developer.
The ability of imagewise ultrasound exposure in the presence of a transport liquid
and a solute to render the internally fogged element capable of being developed in
a surface developer, particularly at the low ultrasonic energy levels employed, has
never before been recognized as possible or achieved by those skilled in the art.
[0044] In the sequential mode the surface developer is not brought into contact with the
internally fogged element until ultrasonic imagewise exposure is completed. It has
been observed that a significant increase in the imaging sensitivity of this process
is achieved if development follows ultrasonic exposure. Specifically, it has been
observed that a significant enhancement in density differences between ultrasonically
exposed and background areas can be achieved when development is delayed from 10 to
200 seconds (optimally from 15 to 50 seconds) following ultrasonic exposure at ordinary
room temperature (20 to 25°C). This enhancement of the ultrasonographic image is attributed
to a furtherance during the delay period of the alterations of the internally fogged
element initiated by ultrasonic exposure.
[0045] In an alternative form of this process the internally fogged silver halide element
is imagewise ultrasonically exposed while in contact with an internal developer. Internal
developers are those capable of developing silver halide grains which contain an internal
latent image or internal fog. One conventional approach of ascertaining if a developer
is an internal developer is to light expose an internal latent image-forming silver
halide emulsion and then to bleach the surface of silver halide grains to remove any
surface fog. If the developer is capable of producing a substantial density by development
of surface bleached silver halide grains, it is an internal developer. In quantitative
terms, preferred internal developers are those which produce a density of at least
0.5 within 5 minutes at 25°C in a silver halide element useful in the practice of
this process which has been light exposed to provide a maximum density and then bleached
for 5 minutes at 25°C in a 0.3 percent aqueous solution of potassium ferricyanide.
Conversely, developers which fail to produce a density of at least 0.5, preferably
0.1, are preferred surface developers. Among the advantages of imagewise ultrasonic
exposure in the presence of an internal developer are that imaging can be readily
achieved with minimal ultrasonic energy levels and only a single processing solution
is employed for both ultrasonic exposure and development. However, care must be exercised
to avoid extended contact of the element with the internal developer, since this can
result in background fog.
[0046] In another sequential form of this process the internally fogged silver halide element
is imagewise ultrasonically exposed in a silver halide solvent as described above,
such as a thioether, thiosulfate, thiocyanate or, in the case of high chloride silver
halide grains, a sulfite, and in the absence of a developer. By increasing the solvent
action on the silver halide grains being ultrasonically exposed, such as by using
higher ultrasonic energy levels, longer exposure periods, higher solute concentrations
or some combination of these, the silver halide grains in ultrasonically exposed areas
can be substantially entirely dissolved. In areas where ultrasonic exposure does not
occur the silver halide grains may be unaffected by the silver halide solvent or,
preferably, the silver halide grains can be sufficiently modified by the solvent that
they become developable in a surface developer. In the former case the silver halide
grains are thereafter developed in an internal developer while in the latter case
the silver halide grains can thereafter be developed in either a surface or an internal
developer. Development produces little or no density in ultrasonically exposed areas,
since the silver halide in exposed areas has been dissolved and removed, whereas the
developer readily develops the internally fobbed silver halide grains in the areas
which are not ultrasonically exposed. The result is a reversal or positive image,
that is, a maximum density is produced in areas of the elements which are not ultrasonically
exposed. By carefully limiting both the degree of silver halide dissolution in the
ultrasonic exposure step and the development step, it is possible alternatively to
produce a negative image by this process mode, but such a form of the ion is not preferred,
since high background densities are to be expected.
[0047] This process can be practiced with any conventional surface or internal developer.
The surface developers can be converted to internal developers by incorporating silver
halide solvents, such as thioethers, thiosulfates and thiocyanates, water soluble
iodide salts or, in the case of high chloride silver halides, water soluble sulfites
in the solute concentrations disclosed above or as ascertained by the solute selection
test procedures.
[0048] It should be pointed out that while ultrasonic exposure times can be quite low, in
the order of a few seconds or less, once the internal fog within the silver halide
grains has been revealed by the action of ultrasonic exposure acting in conjunction
with the transport liquid and solute, the rates of development are those that would.be
expected from a knowledge of photographic development procedures. Accordingly, in
the modes of ultrasonic exposure in the presence of a developer, it is apparent that
ultrasonic exposure will be completed well before optimum development of the elements
has been achieved. Because ultrasonic exposure periods will ordinarily be so low as
to be negligible in comparison with total development times, development periods in
both the sequential and concurrent exposure- development modes will typically be those
experienced in conventional photographic development, typically from 30 seconds to
10 minutes, most commonly from 1 to 5 minutes.
[0049] An optimum imaging response for any specific system described above can be achieved
by routine adjustments. For example, the solubility of silver chloride is higher than
that of silver bromide which is in turn higher than that of silver iodide, and this
permits weaker silver halide solvents and/cr lower solvent concentrations to be employed
with silver chlorides than with silver bromides and silver bromo- iodides. In addition
to the variance in the activity levels of silver halide solvents, there is a wide
variance in the activity levels of silver halide solvents. The choice and concentration
levels of the silver halide solvents are also influenced by whether a negative ultrasonographic
image is being formed, in which instance the silver halide solvent acts in ultrasonically
exposed areas to reveal the internal fog sites in the silver halide grains, or a positive
ultrasonographic image is being formed, in which instance the solvent acts to dissolve
the silver halide grains in exposed areas. For negative-working ultrasonographic imaging
it is preferred to employ silver halide solvents such as thioethers, thiosulfates,
thiocyanates and pyridinium salts of the type described in concentrations of from
0.1 to 30 grams per liter of transport liquid, with concentrations of from 0.5 to
5.0 grams per liter being specifically preferred for thiosulfates and concentrations
of from 5 to 15 grams per liter being specifically preferred for thiocyanates. Higher
concentration levels can be employed in producing positive ultrasonographic images
with these solvents. For sulfite solutes negative ultrasonographic images in silver
chloride emulsions can be obtained with preferred concentrations in the range of from
10 to 50 grams per liter, while positive ultrasonographic images can .be obtained
with preferred concentrations in the range of from 80 to 100 grams per liter.
[0050] The preferred solute concentration ranges set forth above assume conventional ratios
of the internally fogged silver halide grains to vehicles, typically in the range
of from 1:2 to 2:1, on a weight basis. Since the vehicle provides an impedance to
the diffusion of the solute, it is apparent that adjustment of the proportion of the
vehicle and its permeability, as by hardening, can be relied upon to control the diffusion
rate of the solute, or, conversely, the concentration of the solute can be varied
to adjust the rate of response of a selected internally fogged element. For example,
if an internally fogged element responds too rapidly to the solute for convenient
handling, its rate of response can be decreased merely by overcoating the emulsion
layer with a vehicle overcoat or by reducing the concentration of the solute in the
transport liquid.
[0051] A preferred negative-working system will, in the absence of ultrasound, within a
period of from 10 seconds to 10 hours of contact with the transport liquid containing
the solute cause the internally fogged element to produce a density of at least 0.5,
preferably at least 1.0, when thereafter developed in a surface developer, such as
Reference Surface Developer B, for 5 minutes at 25°C. If the density is achieved in
less than 10 seconds in the absence of ultrasound, reproducible imaging will be difficult
without obtaining high background densities or without employing high speed transport
equipment for bringing the internally fogged element into and out of contact with
the solute, although this is, of course, possible. On the other hand, if a density
of at least 0.5 is not obtained within 10 hours following contact of the solute with
the internally fogged element, the process will be unattractively slow when ultrasound
is employed at lower power levels, such as-are preferred in the practice of this process.
[0052] Similarly, a preferred positive-working system will, in the absence of ultrasound,
within a period of from 10 seconds to 10 hours of contact with the transport liquid
containing the solute cause the internally fogged element to produce a density of
at least 0.5 less, preferably at least 1.0 less, when thereafter developed in an internal
developer, such as Reference Internal Developer A, for 5 minutes at 25°C, than the
density produced in an identical element which is otherwise similarly processed, but
which is not placed in contact with the transport liquid containing the solute.
[0053] It is recognized that in at least some instances identical elements can be used to
produce either positive or negative ultrasonographic images, merely by adjusting silver
halide solvent concentrations and/or ultrasonic exposure levels, and the very same
solvent concentrations and ultrasonic exposure levels can produce either positive
or negative ultrasonographic images by varying the silver halide and/or vehicle of
the internally fogged elements being employed.
[0054] It is specifically recognized that the internally fogged elements employed, particularly
the silver halide emulsion layers thereof employed in imaging, can be protected against
the production of surface fog. Conventional antifoggants and stabilizers, which can
be used alone or in combination include the thiazolium salts, azaindenes, mercury
salts, urazoles, sulfocate- chols, oximes, nitron, nitroindazoles, mercaptotetrazoles,
polyvalent metal salts, thiuronium salts, and palladium, platinum and gold salts.
[0055] The viewable image produced in each of the various modes of practicing this process
can be either a silver image, a dye image or a combination of both. Dye images can
be formed through the use _of a color developer composition and color couplers, for
example. The color couplers can be incorporated in either the developer composition,
as in the case of mobile couplers, or in the ultrasonographic element, as in the case
of ballasted couplers. Ballasted couplers .are typically incorporated directly in
the imaging silver halide emulsion layer or in a layer adjacent thereto. Generally
any color image-forming approach which makes use of a silver image can be employed
in the practice of my process. Color materials are discussed, for example, in paragraph
XXII, Product Licensing Index, Vol. 92, December 1971, publication 9232. Both Product
Licensing Index and Research Disclcsure are published by Industrial Opportunities,
Homewell, Havant Hampshire, P09 iEF, United Kingdom.
[0056] It is specifically contemplated that the elements can produce dye images through
the selective removal of dyes. Negative or positive dye images can be produced by
the immobilization or mobilization of incorporated color-providing substances as a
function of exposure and development, as illustrated by U.S. Patents 2,543,691; 3,227,552;
3,443,940; 3,549,364; 3,620,730; 3,730,718; 3,923,510; 4,052,214; and 4,076,529; and
U.K. Patents 1,456,413; 1,479,739; 1,475,265 and 1,471,752.
[0057] The internally fogged elements can contain hardeners for the hydrophilic colloid
layers, as described in paragraph VII plasticizers, lubricants, coating aids and matting
agents, as described in paragraphs XI, XII and XIII Product Licensing Index, publication
9232, cited above.
[0058] The photographic layers, including the silver halide emulsion layers and other layers
of the elements can be coated on a wide variety of supports. Typical supports include
cellulose nitrate film, cellulose acetate film, poly(ethylene terephthalate)film,
polycarbonate film and related films or resinous materials, as well as glass, paper,
metal and the like. Typically, a flexible support is employed, especially a paper
support, which can be partially acetylated or coated with baryta and/or an alpha-olefin
polymer, particularly a polymer of an alpha-clefin containing 2 to 10 carbon atoms
such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
[0059] Well known processing techniques and procedures can be employed. For example, the
pH of the developer can be reduced to stop development, as by the use of a conventional
stop bath. Where a surface developer is employed, pH reduction to stop development
can be readily omitted without adverse effect in most instances. Where a dye image
is formed, the silver image in the photographic element can be removed by bleaching
or blixing. While fixing of the silver halide can be undertaken, the lack of light
sensitivity of the silver halide in most instances renders this step unnecessary.
Processing formulations and techniques are described in L. F. Mason, Photographic
Processing Chemistry, Focal Press, London, 1966; Processing Chemicals and Formulas,
Publication J-1, Eastman Kodak Company, 1973; Photo-Lab Index, Morgan and Morgan,
Inc., Dobbs Ferry, New York, 1977, and Neblette's Handbook of Photography and Reprography
- Materials, Processes and Systems, Van-Nostrand Reinhold Company, 7th Ed., 1977.
[0060] Included among the processing methods are web processing, as illustrated by U.S.
Patent 3,179,517; stabilization processing, as illustrated by U.S. Patents 3,220,839,
3,647,453 and 3,615,511 and U.K. Patent 1,258,906; monobath processing and described
in Haist, Monobath Manual, Morgan and Morgan, Inc., 1966, U.S. Patents 3,240,603,
3,615,513, 3,628,955 and 3,723,126; infectious development, as illustrated by . U.S.
Patents 3,294,537, 3,600,174, 3,615,519, 3,615,524 3,516,830, 3,615,488, 3,625,689
and 3,708,303, and U.K. Patent 1,273,030; hardening development, as illustrated by
U.S. Patent 3,232,761; roller transport processing, as illustrated by U.S. Patents
3,025,779, 3,515,556, 3,573,914 and 3,647,459, and U.K. Patent 1,269,268; alkaline
vapor processing, as illustrated by Product Licensing Index, Vol. 97, May 1972, Item
9711, U.S. Patents 3,816,136 and 3,985,564; metal ion development as illustrated by
Price, Photographic Science and Engineering, Vol. 19, Number 5, 1975, pp. 283-287
and Vought, Research Disclosure, Vol. 150, October 1976, Item 15034; reversal processing,
as illustrated by U.S. Patent 3,576,633; and surface application processing, as illustrated
by U.S. Patent 3,418,132.
[0061] Dye images which correspond to the silver halide rendered selectively developable
by imagewise exposure, typically negative dye images, can be produced by processing,
as illustrated by the Kodacolor C-22 the Kodak Flexicolor C-41 and the Agfacolor processes
described in British Journal of Photography Annual, 1977, pp. 201-205. The photographic
elements can also be processed by the Kodak Ektaprint-3 and -300 processes as described
in Kodak Color Dataguide, 5th Ed., 1975, pp. 18-19, and the Agfa color process as
described in British Journal of Photography Annual, 1977, pp. 205-206.
[0062] The photographic elements can be processed in the presence of reducible species,
such as transition metal ion complexes (e.g. cobalt (III) and ruthenium (III) complexes
containing amine and/or amine ligands) and percxy compounds (e.g. hydrogen peroxide
and alkali metal perborates and perearbonates).
[0063] Dye images can be formed or amplified by processes which employ in combination with
a dye-image- generating reducing agent an inert transition metal complex oxidizing
agent, as illustrated by U.S. Patents
3,
748,138;
3,826,652; 3,862,842; 3.989,526 and 3,765,891, and/or a peroxide oxidizing agent, as
illustrated by U.S. Patent 3,674,490, Research Disclosure, Vol. 116, December 1973,
Item 11660, and Bissonette, Research Disclosure, Vol. 148, August 1976, Items 14836,
14846 and 14847. The photographic elements can be particularly adapted to Form dye
images by such processes, as illustrated by U.S. Patents 3,822,129; 3,834,907; 3,847,619;
3,902,905 and 3,904,413.
[0064] The presence of transition metal ion complexes can accelerate silver halide development,
as illustrated by U.S. Patents 3,748,138; 3,901,712 and 3,964,912; can bleach silver
images, as illustrated by Bissonette U.S. Patent 3,923,511 and Research Disclosure,
Item 14846, and can be employed to form tanned colloid images, as illustrated by U.S.
Patents 3,856,524 and 3,862,855.
[0065] The developers and elements can contain organic or inorganic developing agents or
mixtures thereof. Examples of useful organic developing agents include hydroquinones,
catechols, aminophenols, pyrazolidones, phenylenediamines, tetrahydroquinolines, bis(pyridone)-amines,
cycloalkenones, pyrimidines, reductones, and coumarins. Useful inorganic developing
agents include compounds of a metal having at least two distinct valence states which
is capable of reducing ionic silver to metallic silver. Such metals include iron,
titanium, vanadium and chromium, and the metal compounds employed are typically complexes
with organic compounds such as polycarboxylic acids or aminopolycarboxylic acids.
Particularly useful developing agents include the iodohydroquinones of U.S. Patent
3,297,445, the amino hydroxy cycloalkenones of U.S. Patent 3,690,872, the 5-hydroxy
and 5-amino pyrimidines of U.S. Patent 3,672,891, the N-acyl derivatives of p-aminophenols
of British Patent 1,045,303, the 2-acyl and 3-acyl derivatives of 3-pyrazolidones
of British Patent 1,023,701, the 2-hydroxyalkyl and 2-aminoalkyl-3-pyrazolidones of
U.S. Patent 3,241,967, the anhydro dihydro reductones of U.S. Patent 3,672,896, and
the 6-hydroxy and 6-amino coumarins of U.S. Patent 3,615,521. Advantageous results
can be obtained with combinations of organic and inorganic developing agents as described
in Vought, Research Disclosure, Vol. 150, October 1976, Item 15034, and with combinations
of different types of organic developing agents such as the combination of anhydro
dihydro amino reductones and aminomethyl hydroquinones of U.S. Patent 3,666,457 and
the combination of ascorbic acid and 3-pyrazolidone of British Patent 1,281,516. Developing
agents can be incorporated in the elements in the form of precursors. Examples of
such precursors include the halogenated acyl hydroquinones of U.S. Patent 3,246,988,
the N-acyl derivatives of aminophenols of U.S. Patent 3,291,609, the reaction products
of a catechol or hydroquinone with a metal described in U.S. Patent 3,295,978, the
quinhydrone dyes of U.S. Patent 3,565,627, the cyclohex-2-ene-1,4-diones and cyclohex-2-ene-1-one-4-monoketals
of U.S. Patent 3,586,506, and the Schiff bases of p-phenylenediamines of Pupo et al,
Research Disclosure, Vol. 151, November 1976, Item 15159.
[0066] The developing agents can be present in one or more hydrophilic colloid layers of
the elements, such as a silver halide emulsion layer or a layer adjacent the emulsion
layer. The developing agent can be added to the layer in the form of a dispersion
with a film- forming polymer in a water immiscible solvent, as illustrated by U.S.
Patent 3,518,088, or as a dispersion with a polymer latex, as illustrated by Research
Disclosure,
Vol. 159, July 1977, Item 15930, and Research Disclosure, Vol, 148, August 1976, Item
14850.
[0067] The elements and developers can contain development modifiers either to accelerate
or restrain development.
[0068] Development accelerators of the poly(alkylene oxide) type can be used. Representative
development accelerators additionally comprise carboxylic and sulfonic acid compounds
and their salts, aliphatic amines, carbamates, adducts of a thioamine with an aldehyde,
polyamines, polyamides, polyesters, aminophenols, polyhydroxybenzenes, thioethers
and thioamides, poly(vinyl lactams), poly(N-vinyl-2-oxaolidone), protamine sulfate,
pyrazolidones, dihydropyridine compounds, hydroxyalkyl ether derivatives of starch,
sulfite ester polymers, bis-sulfonyl alkanes, 1,4-thiazines and thiocarbamate. Representative
development accelerators also comprise cationic compounds, disulfides, imidazole derivatives,
inorganic salts, surfactants, thiazolidines and triazoles.
[0069] Representatives of development restrainers that can be used include cationic compounds,
esters, lactams, mercaptans and thiones, polypeptides, poly(alkylene oxide) derivatives,
sulfoxides, thiazoles, diazcles, triazoles and imidazoles.
[0070] It is contemplated that the ultrasonic exposure, development and other photographic
processing steps of this process can be practiced within the temperature ranges conventionally
employed in photography. The elements can be washed to remove solute after ultrasonic
exposure and before development, if desired, in the sequential modes of practicing
this invention.
[0071] The invention is further illustrated by the following examples:
Example 1
[0072] A converted-halide gelatino silver bromochloride emulsion (91 mole percent bromide,
9 mole percent chloride based on total halide), prepared according to Example 1 of
U.S. Patent 2,592,250, was internally light fogged and coated on a polyester film
support to obtain silver coverage of 3.2 g/m
2 and gelatin coverage of
3.
2 g
/m2.
[0073] The resulting ultrasonographic element was divided into identical strips for separate
exposure in an j ultrasonic sensitometer.
[0074] The ultrasonic sensitometer was made up of a rectangular plastic vessel open at its
top and adapted to contain a liquid reservoir. Arranged along the bottom wall of the
vessel were seven identical ultrasonic transducers. The ultrasonic transducers each
presented a circular emitting surface of 0.785 square centimeters, as viewed from
above, and were arranged in a row, adjacent transducers being separated by 2.4 cm.
The emitting surfaces of the transducers were in contact with the liquid in the reservoir.
The ultrasonic frequency supplied to the transducers was 5 megahertz. Each strip to
be tested was immersed in the reservoir just beneath its surface and held spaced from
the transducers by about 15.0 cm using a suitable clamp to hold the strip flat and
in position.
[0075] Six strips of the ultrasonographic element were immersed in the reservoir for 15
seconds before ultrasonic exposure, exposed imagewise while immersed to ultrasonic
energy for 10 seconds at 2.5 watts/cm
2 and then left immersed for 2 minutes. Kodak Developer D-19 modified to concentrations
of potassium iodide of 0, 50, 100, 125, 150 and 175 mg potassium iodide per liter
of developer was used as the liquid in the reservoir. For potassium iodide concentrations
of up to 100 mg per liter of developer, the minimum density in background areas remained
constant at a value of approximately 0.1 density unit. In image areas a sharp increase
in density was observed at potassium iodide concentrations above 50 mg potassium iodide
per liter of developer. At a concentration of 100 mg of potassium iodide per liter,
the maximum density was approximately 1.4 with a minimum density of approximately
0.1, and at a concentration of 175 mg potassium iodide per liter the density was approximately
3.9 with a minimum density of approximately 1.2.
[0076] The procedure above was repeated using two identical strips, but the strips were
immersed for 10 seconds prior to ultrasonic exposure, exposed for 10 seconds and left
immersed for 2 minutes. The strips were processed in Kodak Developer D-19 modified
to contain potassium iodide of 100 and 125 mg potassium iodide per liter of developer,
respectively. In Figure 1, Curve A shows the negative ultrasonographic characteristic
curve obtained with the lower KI concentration and Curve B shows the corresponding
curve for the higher KI concentration.
[0077] Six identical strips, without prior ultrasonic exposure, were processed in Kodak
Developer D-19 modified to contain potassium iodide concentration of 100 mg of potassium
iodide per liter of developer, at increasing immersion times of 1, 2, 3, 4, 5 and
6 minutes, respectively, at 25°C. Figure 2 shows the curve obtained by plotting density
versus immersion time in seconds.
Example 2
[0078] Two strips of the ultrasonographic element described in Example 1 were exposed in
the ultrasonic sensitometer. The liquid reservoir was filled with water. Each strip
was immersed in the reservoir for 10 seconds before ultrasonic exposure. Exposure
was to pulsed ultrasonic energy of 10
-6 second pulse density and 10 second intervals between pulses. The first strip was
exposed for 10 seconds with a power output of the seven transducers at the film plane
of 35, 8.9, 2.2, 0.55, 0.25, 0.08 and 0.031 watts/cm
2. The second strip was exposed for 30 seconds at twice the transducer power output
used to expose the first strip. Both strips were left immersed for sixty seconds after
exposure. Both strips were processed in Kodak Developer D-19 for 3 minutes, fixed,
washed and dried. The processed strips were clear and transparent. No images were
present.
[0079] Using two additional strips the above procedure was repeated, except as specifically
noted. The water in the reservoir contained 400 mg per liter potassium iodide. The
strips were imagewise exposed to ultrasonic energy for 30 seconds and left immersed
for 40 seconds. The power output transducers for the third strip was the same as for
the first strip. The power output of the transducers for the fourth strip was reduced
by half as compared to the exposure of the first strip. High density regions corresponding
to all seven transducers could be discerned in the third strip. Six regions corresponding
to the higher powered transducers could be visually detected on the fourth strip.
The size and density of each region on the fourth strip was less than the corresponding
one on the third strip. A moderate background density was obtained, which was the
same in both strips. Figure 3 is a plot of density vs. peak ultrasonic intensity (in
mw/cm
2) for the third and fourth strips.
Example 3
[0080] Twelve strips of the ultrasonographic-element of Example 1 were used in this example.
They were exposed as in Example 2 in the reservoir containing water plus potassium
iodide at varying concentrations. Total ultrasonic exposure was 10
5 pulses so that the ultrasonic exposure was the same for all strips. Power output
of the transducers was the same as for the first strip of Example 2. Besides the concentration
of potassium iodide, only the length of time the strips were left immersed after exposure
was varied. Table I below shows the variations in exposure conditions for the strips,
numbered 1 to 12. The strips were processed as in Example 2.
[0081] As shown in Figure 4, image density increased with increasing iodide ion concentration
and to a lesser degree with increasing immersion time after exposure. Background density
also increased with increasing iodide ion concentration and with increasing immersion
time after exposure. The gain in image density generally was less than the gain in
background density with increasing immersion time so that in all four concentration
series, the best image descrimination was obtained with the shortest immersion time
after exposure. In this series, the 400 mg/l KI bath gave the greatest image descrimination.
Example
[0082] Two strips A and B of the ultrasonographic element of Example 1 were exposed and
processed similarly as the third strip in Example 2, except that exposure was carried
out in water plus potassium thiocyanate in the reservoir of the ultrasonic sensitometer.
The concentration of the thiocyanate was 10 g/l. The strips were exposed to ultrasonic
energy and left immersed after exposure for the times shown below in Table II. The
characteristic curves are shown in Figure 5. Good ultrasonic negative images were
produced.
[0083] Two strips C and D were exposed as above in the reservoir containing dissolved potassium
thiocyanate (20 g/1) and were processed in Kodak Developer D-19. One strip was removed
immediately after exposure and the other was left immersed for 30 seconds following
ultrasonic exposure, as shown below in Table II. The characteristic curves are shown
in Figure 5.
[0084]
Example 5
[0085] Experiments similar to those of Example 4 were conducted to illustrate regions with
ultrasonic exposure using an aqueous potassium thiosulfate solution in the reservoir.
At concentrations of 1.25 to 2.50 g/l of thiosulfate, ultrasonic exposures were made
using the same transducer power levels as for the third strip of Example 2 with ultrasonic
exposure for 30 seconds. The strips were processed in Kodak Developer D-19 for three
minutes, fixed, washed and dried. An ultrasonic characteristic curve was obtained
exhibiting acceptable maximum densities and low minimum densities.
Example 6
[0086] Figure 6 shows ultrasonic characteristic curves for two strips of the ultrasonographic
element of Example 1 exposed similarly as the third strip in Example 2, except that
the strips were exposed in an aqueous potassium iodide solution (400 mg/1) and processed
in Kodak Developer D-19 for three minutes. Both strips were immersed for 10 seconds
before exposure, exposed to pulsed ultrasonic energy of 10
-6 second pulse duration, 10
-5 second intervals between pulses and were left immersed for 60 seconds after exposure.
The first strip (A) was given 10 pulses (1 second total exposure) and the second strip
(B) was given 10
5 pulses (10 seconds total ultrasonic exposure). The greater maximum density was obtained
on the second strip.
Example 7
[0087] A 0.68 micron silver chloride core-shell emulsion was coated on a polymeric film
support to achieve silver coverage of 2.5 g/m
2 and gelatin ccver- age of 4.3 g/m
2. Strips of the coating were ultrasonically exposed and developed under varying conditions.
Exposure was carried out in the ultrasonic sensitometer of Example 1. Actual exposures
in this example were to higher power outputs at 400, 200, 110, 40, 25, 8 and 2.7 watts/cm2
or lower power outputs at 80, 25, 10, 4, 2.2, .75 and .27 watts/cm2.
[0088] Eight strips of the ultrasonographic element were exposed to pulsed ultrasonic energy
(10
-6 pulse width, 10 pulse period and 10
5 pulses) in a solution of potassium sulfite (K
2SO
3) in water and developed as shown below in Table III. Development time was six minutes
at 20°C. The coatings were then fixed, washed and dried.
[0089] Strips 1 and 2 showed slight negative images corresponding to the most powerful transducers.
Background density was light gray. Strips 3 and 4 showed no images. They were uniformly
dark. Strips 5 and 6 showed faint reversal images corresponding to the most powerful
transducers. Strips 7 and 8 showed strong reversal images varying in size in proportion
to the power range of the corresponding transducers.